Theoretical reduction potentials for nitrogen oxides from CBS-QB3 energetics and (C)PCM solvation calculations

Andrew S Dutton; Jon M Fukuto; Kendall N Houk

doi:10.1021/ic048734q

Theoretical reduction potentials for nitrogen oxides from CBS-QB3 energetics and (C)PCM solvation calculations

Inorg Chem. 2005 May 30;44(11):4024-8. doi: 10.1021/ic048734q.

Authors

Andrew S Dutton¹, Jon M Fukuto, Kendall N Houk

Affiliation

¹ Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, USA.

PMID: 15907131
DOI: 10.1021/ic048734q

Abstract

The complete basis set method, CBS-QB3, is used in combination with two continuum solvation models for aqueous solvation to compute reduction potentials previously determined experimentally for 36 nitrogen oxides and related species of the general formula H(V)C(W)N(X)O(Y)Cl(Z). The PCM model led to the correlation E(o)exp (vs NHE) = 0.84E(o)calc + 0.03 V with an average error of 0.12 V (2.8 kcal/mol) and a maximum error of 0.32 V (7.4 kcal/mol). The CPCM/UAKS model gave E(o)exp (vs NHE) = 0.83E(o)calc + 0.11 V with the same average error. This general method was used to predict reduction potentials (+/-0.3 V) for nitrogen oxides for which reduction potentials are not known with certainty: NO2/NO2- (0.6 V), NO3/NO3- (1.9 V), N2O3-/N2O3(2-) (0.5 V), HN2O3/HN2O3- (0.9 V), HONNO,H+/HONNOH (1.6 V), 2NO,H+/HONNO (0.0 V), 2NO/ONNO- (-0.1 V), ONNO-/ONNO(2-) (-0.4 V), HNO,H+/H2NO (0.6 V), H2NO,H+/H2NOH (0.9 V), HNO,2H+/H2NOH (0.8 V), and HNO/HNO- (-0.7 V).

Publication types

Research Support, N.I.H., Extramural
Research Support, U.S. Gov't, Non-P.H.S.
Research Support, U.S. Gov't, P.H.S.

MeSH terms

Models, Chemical*
Nitrogen Oxides / chemistry*
Oxidation-Reduction
Thermodynamics

Substances

Nitrogen Oxides